Non-flammable aerosol multiuse invert emulsion lubricant

ABSTRACT

Stable water-in-oil emulsions suitable for use as fire-resistant aerosol multipurpose lubricants. The water-in-oil emulsion comprises a synthetic ester base oil, compatible invert emulsifier, water, and a preservative. The aerosol apparatus employs a larger than standard stem orifice to produce a non-flammable aerosol.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 15/946,611,filed Apr. 5, 2018, which claims priority on Provisional U.S.Provisional Patent Application No. 62/482,305, filed Apr. 6, 2017, andU.S. Provisional Patent Application No. 62/623,610, filed Jan. 30, 2018,which are incorporated herein in their entirety by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not Applicable

REFERENCE TO A “SEQUENCE LISTING”, A TABLE, OR A COMPUTER PROGRAMLISTING APPENDIX SUBMITTED ON COMPACT DISC

Not Applicable

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to non-flammable multiuse aerosollubricants.

2. Description of Prior Art Including Information Disclosed Under 37 CFR1.97 and 1.98

This invention relates to an improved aerosol non-flammable compositionin the form of a substantially stable water-in-oil emulsion for use inprotecting metal from rust and corrosion, penetrating stuck parts,displacing moisture and lubricating almost anything. More particularly,such improved aerosol non-flammable composition consists of water, anoil base, an invert emulsifier, and a preservative. The aerosol deliverysystem consists of a standard aerosol mechanism with increased stemorifice radius sufficient to create larger than standard droplets in theaerosol to reduce the flammability profile of the aerosol mist.

Multiuse aerosol lubricants are widely known. Generally, suchcompositions employ hydrocarbons and are flammable. The most widelyknown and successful of these compounds is marketed under the trademarkWD-40®. For over 50 years, consumers have used WD-40® Multi-Use Product(hereinafter “WD-40®”) to protect metal from rust and corrosion and forpenetrating lubrication. WD-40® protects and lubricates effectively, inpart, because it so effectively displaces water. The formulation forWD-40® is a trade secret but is generally understood to consist ofhydrocarbons and other proprietary ingredients. It does not containwater.

There has long been a need for non-flammable multiuse aerosollubricants. However, there is an inherent tension between performanceand non-flammability in multiuse aerosol lubricants. While hydrocarbonsimpart much of the performance in multiuse lubricants like WD-40®, theyare inherently flammable. Additionally, aerosols add to the danger ofcreating a flammable product. Conversely, while water decreases theflammability profile of the product, water causes rust and corrosion,which is exactly what multiuse aerosol lubricants are designed toprevent.

The use of water-in-oil emulsions has been used in other fields tocreate non-flammable lubricants. For example, in the hydraulic field,invert emulsions are routinely used to create non-flammable hydraulicfluids that have lubricating properties. However, because of the higherdemands for lubrication and non-flammability, inverse emulations havenot been used for multiuse aerosol lubricants.

BRIEF SUMMARY OF THE INVENTION

This invention has found surprisingly that when an invert emulsion madewith a synthetic ester base oil and a compatible invert emulsifier isdelivered through an aerosol apparatus that creates certain larger thanstandard droplets it creates a non-flammable multiuse lubricant aerosol.A preservative is included in the composition to prevent the growth ofbacteria, yeast, and molds that would interfere with the creation andstability of the emulsion.

The improved water-in-oil aerosol non-flammable multiuse lubricatingcomposition appears to be an improvement over the prior art lubricatingcompositions because of its improved combination of lubrication,corrosion and rust prevention, water displacement, and fire resistance.

Broadly, the improved multiuse composition is in the form of asubstantially stable water-in-oil emulsion consisting of 10% to 20% byweight of a liquified, normally gaseous, propellant and 80% to 90% of abase consisting essentially of by weight:

A. 45% to 55% of water;

B. 5% to 10% water-in-oil emulsifier compatible with a synthetic esterbase oil;

C. 35% to 45% of synthetic ester base oil; and

D. 0.01% to 1% of preservative.

Also, within the scope of the claimed invention is the aerosol apparatusfor delivering the formulation in a stable non-flammable form. Aerosolsof the current invention created using a standard stem sizes, however,are flammable. The current invention uses stems and actuators withincreased radiuses or other components to create larger droplets in theaerosol, which in turn creates a non-flammable aerosol. Using standardaerosol components, a stem orifice of 0.013″ to 0.025″ is preferable.

DETAILED DESCRIPTION OF THE INVENTION

A multiuse composition in the form of a substantially stablewater-in-oil emulsion consists of 13% Honeywell's Solstice (HFO-1234ze)propellent by weight and 87% to a base consisting essentially of byweight:

A. 51.95% of deionized water;

B. 8% Hypermer 2524;

C. 40% of Priolube LL-564; and

D. 0.05% of Reputain B-30.

The aerosol apparatus for delivering the formulation in a stablenon-flammable form consists of standard aerosol components with a stemwith increased orifice of 0.020″ and two entry ways for uptake of thebase liquid.

Hypermer 2524 is an oligomeric ester emulsifier for use in themanufacture of inverse polymer emulsions. It is compatible withsynthetic esters such as Priolube LL-564 as an inverse emulsifier. It isa proprietary product manufactured and sold by Croda International Plc.

Priolube LL-564 is a low viscosity synthetic ester. It is a proprietaryproduct manufactured and sold by Croda International Plc.

Reputain B-30 is a preservative that contains2-bromo-2-nitropropane-1,3-diol (30%), Propylene glycol (57.5-62.5%),and Water (7-10%).

The above composition has shown surprisingly good lubricating andanticorrosion properties while maintaining non-flammability in both theliquid and aerosol form.

Comparative Testing

The invert emulsion was the only formulation that had lubricating andanticorrosion properties similar to the market leader WD-40®, whileremaining non-flammable in both liquid and aerosol form.

Alternative formulas tested included oil-in-water emulsions, chlorinatedhydrocarbons and perfluoropolyether (PFPE), and phosphate esters,phosphate ester and fluorinated hydrocarbons. Those formulas included:

Synthetic Emulsion—This is a proprietary synthetic metal working fluidformulation provided by Croda International Plc.Semisynthetic Emulsion—This is a proprietary semisynthetic metal workingfluid formulation provided by Croda International Plc.GPL and PFPE—This is a formulation of chlorinated hydrocarbons andperfluoropolyether (PFPE). It consists of 83.3% Vertrel XF (Chlorinatedhydrocarbon),14.7% Acetone, and 2% GPL-105 (PFPE). Vertel XF(1,1,1,2,2,3,4,5,5,5-Decafluoropentane) is a proprietaryhydrofluorocarbon fluid used as a solvent and vapor degreasing equipmentfor cleaning, rinsing, and drying. Vertel XF is supplied by Chemours.GPL-105 is a clear, colorless perfluoropolyether oil that isnonflammable and long-lasting. On a weight basis, GPL-105 contains 21.6%carbon, 9.4% oxygen, and 69.0% Fluorine. It is sourced from Chemours.KDP and PFPE—This is also a formulation of chlorinated hydrocarbons andperfluoropolyether (PFPE). It consists of 83.3% Vertrel XF (Chlorinatedhydrocarbon), 14.7% Acetone, and 2% KDP (PFPE). KDP is the same as GPL,but also contains anti-corrosion additive. It is sourced from Chemours.Phosphate Ester—This is a product sold by Exxon under the name Hyjet V.It is marketed as a fire-resistant hydraulic fluid based on phosphateesters. Its chemical composition is commercially described as 70-80%tributyl phosphate, 10-20% phenol, isopropylated, phosphate, 5-7%aliphatic epoxide, and 0.1-1% 2,6-Di-Tert-Butyl-P-Cresol.Phosphate Ester and Fluorinated Hydrocarbons—It contains 65% Reolube and35% Vertel XF. Reolube 46B is sold by Chemours and marketed as afire-resistant hydraulic fluid. It is essentially 100% Phenol,isobutylenated, phosphate, with less than 25% of phenols triphenylphosphates.

Below is a comparison of the preferred embodiment to the otherprospective multiuse lubricants and WD-40®.

Lubrication Testing

The invert emulsion was generally comparable or better than most of theother potential non-flammable multiuse lubricators. Three tests wereperformed on the formulations to determine their relative abilities tolubricate under varying conditions. Those tests and results aredescribed below.

ASTM D-4172: Wear Preventive Characteristics fo Lubricating Fluid.

This test is commonly known as the Four Ball Wear and measures the wearprotection of a test fluid. Three steel balls are clamped together andcovered with the lubricant to be evaluated. A fourth steel ball ispressed with force into the top cavity formed by the three lower balls.The temperature of the test lubricant can be regulated and then the topball is rotated at 1200 rpm for 60 minutes. Lubricants are compared bythe average of the measure (in mm) of the scar worn into the three lowerballs. Good results are less than 1.0 mm with excellent results beingaround 0.5 mm. Anti-wear fluids will reduce the amount of metal lose dueto friction during a metalworking process or metal to metal contact.

ASTM D-3233: Measurement of Extreme Pressure Properties of FluidLubricants (Falex Pin and Vee Block Methods).

This test measures the load-carrying properties of a lubricant byrotating a steel pin at 290 rpm against two stationary V-blocks immersedin the lubricant sample. Load, in 250 foot pound increments, is appliedto the V-blocks by a ratchet mechanism. The load is increased everyminute until failure occurs as indicated by breakage of the shear pin ortest pin, or inability to increase or maintain the load on the ratchetwheel. Results are reported as pounds with 4,500 being the maximum thatcan be detected. An extreme pressure fluid will maintain its lubricatingproperties as pressure and temperature increases.

ASTM D-5620: Evaluating Thin Film Fluid Lubricants in a Drain and DryMode.

This tests measures the endurance or wear life of a lubricant. The testfluid is deposited on the pin and V-blocks and allowed to drain for 1 to4 minutes. The steel pin is rotated at 290 rpm against two stationaryV-blocks and a load of 300 foot pounds is applied. If after 60 minutes,there is no failure, the load is increased to 500 foot pounds. Failureis when the steady state torque is interrupted by a sharp increase orspike in the torque, breakage of the shear pin, or failure to maintainthe load. Results are reported in minutes at load pounds.

TABLE 1 ASTM Formulation ASTM D-4172 ASTM D-3233 D-5620 Invert Emulsion0.60 mm 3789 lbs 20.5 min WD-40 ® 0.60-0.70 mm     1300-2000 lbs    1-10min Synthetic 0.75 mm 3901 lbs 0.14 min Emulsion Semisynthetic 0.84 mm4500+ lbs   0.32 min Emulsion GPL and PFPE 0.95 mm 1350 lbs  7.5 min KDPand PFPE 2.24 mm 1550 lbs 1.50 min Phosphate Ester 0.62 mm 1900 lbs  5.5min Phosphate Ester 0.59 mm 4500+ lbs   14.7 min and FluorinatedHydrocarbons

Anticorrosion Testing:

The invert emulsion was markedly better than most of the other potentialnon-flammable multiuse lubricators. Two tests were performed on theformulations to determine their relative abilities to prevent corrosionand rust. Those tests and results are described below.

ASTM B-117: Salt Spray (Fog) Apparatus.

This test is used to measure the level of corrosion protection providedby a test fluid. Cold rolled steel panels, with surface prepared by sandblasting, are treated with the fluid by dipping or spray, allowed todrain for 2 hours, then placed in the salt spray cabinet that contains afog of 5% salt (NaCl) water solution at 35° C. (95° F.). Panels are leftin the closed cabinet for the entire test period; we typically use a 72hour period.

FTM-3007: Water Displacement.

This test is used to measure the ability of a fluid to displace water ona metal surface and then provide corrosion protection. Cold rolled steelpanels, with surface prepared by sand blasting, are immersed indeionized water and then immersed in the test fluid just prior to beingplace in a static humidity chamber (25° C. and 50% humidity) for onehour. The procedure is repeated but using the test fluid after a 10%level of water has been added and mixed with it. Results are reported as% visible corrosion for both the as is and the contaminated fluid.

TABLE 2 Formulation ASTM B-117 FTM-3007 Invert Emulsion No Rust at 72Hours No Corrosion on Both WD-40 ® 0-20% Rust at 72 hours   No Corrosionon Both Synthetic Emulsion 87% Rust at 24 Hours No Corrosion on BothSemisynthetic Emulsion 87% Rust at 24 Hours No Corrosion on Both GPL andPFPE 90% Rust at 24 hours Original: 0-1% corrosion. Contaminated: 1-3%corrosion KDP and PFPE 95% Rust at 24 hours Original: 25-50% corrosion.Contaminated: 85-97% corrosion. Phosphate Ester 90% Rust at 24 hoursOriginal: 2-5% corrosion. Contaminated: 2% corrosion Phosphate Ester and95% Rust at 24 Hours Original: 40% corrosion. Fluorinated HydrocarbonsContaminated: 45% corrosion

Flammability Testing:

The invert emulsion was the only potential non-flammable multiuselubricant with superior lubrication and anticorrosion properties thatwas also non-flammable in an aerosol form. The Invert Emulsion wastested for flammability using a straw connected the actuator andwithout. Three tests were performed on the formulations to determinetheir relative flammability profile. Using the larger stem orificeradius reduced the flammability profile of the invert emulsion. Thosetests and results are described below.

Flame Extension and Flashback (outlined in CFR Part 16 1500.45)

A spray can is placed in a holding device 15cm from an open flame sourceset at a height of 5 cm. The spray can is discharged for 5 seconds andthe flame extension is measured. The operator can then determine if aflashback exists by observing if a flame travels backwards toward thespray can.

GHS UN Ignition Distance (performed per UNECE Part III 31.4)

A spray can is discharged towards an open flame starting at a distanceof 60 cm. The distance is shortened incrementally until a sustainedignition is observed.

Enclosed Space Ignition (performed per UNECE Part III Section 31.5)

A spray can is discharged into a test vessel (55 gallon drum) containinga burning candle. A timer is started at the time the can was dischargedin order to determine the time elapsed before ignition, if any.

TABLE 3 Flame Extension GHS UN Ignition Enclosed Space Formulation andFlashback Distance Ignition Invert Emulsion 18 inch flame (no 30 cm (nostraw) >300 s/m3 (Standard Aersol straw) <15 cm (with straw) with 0.013Stem) No flame (with straw) No flashback Invert Emulsion No flameextension No flame >300 s/m3 (Aersol with 0.02″ No flashback Stem)WD-40 ® Produces a flame Greater than 15 cm <300 s/m3 extension andflame flashback Synthetic Emulsion No flame extension No flame >300 s/m3No flashback Semisynthetic No flame extension No flame >300 s/m3Emulsion No flashback GPL and PFPE No flame extension No flame >300 s/m3No flashback KDP and PFPE No flame extension No flame >300 s/m3 Noflashback Phosphate Ester No flame extension No flame >300 s/m3 Noflashback Phosphate Ester and No flame extension No flame >300 s/m3Fluorinated No flashback Hydrocarbons

While only a limited number of preferred embodiments of the presentinvention have been disclosed for purposes of illustration, it isobvious that many modifications and variations could be made thereto. Itis intended to cover all of those modifications and variations whichfall within the scope of the present invention, as defined by thefollowing claims:

We claim:
 1. An aerosol lubricating composition comprising by weight:45% to 55% of water; 5% to 10% water-in-oil emulsifier compatible with asynthetic ester base oil; 35% to 45% of synthetic ester base oil; and apreservative.
 2. The composition of claim 1 in which the water-in-oilemulsifier is an oligomeric ester emulsifier.
 3. The composition ofclaim 1 in which the base oil is a low viscosity synthetic ester.
 4. Thecomposition of claim 1 in which the water is deionized.
 5. Thecomposition of claim 1 in which the composition is provided in anaerosol delivery mechanism with a stem and actuator of sufficient widthradius to a create non-flammable mist.
 6. The composition of claim 5 inwhich the stem width radius is between 0.013″ to 0.025″.
 7. Thecomposition of claim 5 in which the stem width radius is 0.020″.
 8. Thecomposition of claim 1 in which the composition is mixed with anon-flammable propellent in a ratio of 10% to 20% propellent and 80% to90% composition.
 9. The composition of claim 1 in which the compositionis mixed with a non-flammable propellent in a ratio of 13% propellentand 87% composition.
 13. The composition of claim 11 in which thepropellent is Honeywell's Solstice (HFO-1234ze).